Academic performance and learning contexts among children and youth in poverty are central to understanding educational inequalities. Using three waves of data from the Taiwan Database of Children and Youth in Poverty and drawing on the access/mobilization distinction in social capital theory, this study examined agency, intimate upward reference contexts, and top-tier academic standing among secondary school students in poverty. Agency is measured in terms of life satisfaction, learning engagement, and educational aspirations. In the access-oriented pathway, higher learning engagement and educational aspirations predicted a lower likelihood of later experiencing high-intensity intimate upward reference contexts. These contexts were associated with a lower likelihood of top-tier academic standing. In the mobilization-oriented pathway, these contexts showed no supportive indirect effect and a negative direct association in the life satisfaction model. Therefore, having a best friend with higher grades constitutes a complex relational context involving both resource potential and pressure.